Anthracene compounds and coloring-matters and process of making same.



cnnwn OSCAR EAL 32', F MANNHEIM, GERMANY, ASSTIG-BIOE EEG ANKLE SODA FABRIK, OF LUDY'VIGSHAFEN-ON-THE-RHYME, GFJEE'IANY, A. ZDFFEK3JELATXOI-1 AN TEE-110E313 CO'MPOUNYJS AND GGLORING-BATTERS 1 33 PRQQESS @F IJKALI ZIH i31- ZEATLWLE.

Specification of Letters 'iatcn't.

Patented Jinn-c 32",

4 Ho Drawing. original application filed March 5, k318 ficr ial M mi 4-. Ilividcd and thia acclimation filed November 3, 131

To all whom 25 may concco n:

it linownihat I, OSCAR BALL'I, Ph. D,

chcmist, citizen of the Swiss Rcpnblic, i'c- Sui-n42- (which invention is. divided out of my application for Lc ttci's Pzitcnt filed March 5,1910, Serial/No. 547,414,) and of Which the following is a specification.

This invention relates to the production of compounos and coloring matters of tho zinthroccne series.

I have discovered that new condcnsution products of the mithraccnc series of the type indicaiied by the general formula A(S-R-CUOH) as hereinafter defined can be. obtained by causing an :icid-suhsi'ituted aniln'uquinone derivative which conl'uins one or mom than one: Sill'fliltlliilllg' group or uiom (for instance halogenated undu'uquinouc) to rcfici upon a iiliiophcnolwarhoxylic ncid body, and limb ihiirsc condcusulion products in i'hc production. of which an ortho-thiw plicnoi-cizi-hoxylic acid body has been cn1- pioycd can be subjected to furthcr condensation, yielding products which are .anilu'w quinonc thioxonthones and, either in the sulfonaaic-d form or in the unsulionotcd form, nun he used as coloring" matters.

The now condensation products as hero inhcforc sot forth possess a constitution corresponding to The general formula JMS-IbCOOi-D in which A indicates an imthincuiinone rcsiduc, including; a suhstitutcd unthruquinonc residue, R is a simple, or Sllbfiiliflifid, zu'omuiic residue, and althongi'i I express the ncw products of this formula free acids, the metal salts or others with ulli'yl or aryl groups are equivalcnh while u indicates that one or more of the some or different residues may enter into the molecule.

Among tho ihiophenol-cm'hoxylic 'acid hodics which can be used according to my invcniion I include lhioplicnol-curboxylic acids lhcmsoli'cgor u dci-imtive ofnny one of thcsc compounds for instance u salt, or color; thm'cof. Under the term substituted anihrin' uinonc residue in this specification I do not include compounds in which the two carbonyl groups are not intact, such for instance as bcnzunbhrone compounds thrapyridone, compounds, since cc :qvplication claiming the use of such com pounds has been filed, Serial No. 619,105.

If ,the above mentioned L chicgzhenol-canhoxylic acids be used in *bl'ic free stoic for the coni'lcnszition, the corhoxylic acid group is liable to be split off to a certain cxtent, and to this extent uncarhcX /laicd compounds are obtained, but when thcsiilts o e used in this condensation, the desired curb-oxyluicd condensation QOTIIPO'GiauS ohizoncd SiHOUiillY, When prcpan'ng the new con dcnsu'ition coin-pounds ccccrdi I this invcntion from halogenated antl'lmquinoncs containing more than one groportion loci-- oocn, it is possible fil'Su to replace a portion of the halogen using one of the thiopiicnolcui'hox iii acid compounds, and then m rcpiacc :1 further portion with the some GT diii'crcni ihiophcnol-carboxylic acid cocpound, so that in this Way mixed oondcnsoi'ion products can he obtained. ifhc Eccetion can he applied to tho deri' anil'u'aquinonc iiscli' which contain an acid substituting group, and the condo; ii-ion be effected with or without the addi substance which acl's catnlytically.

'lhc condensation products obtainable according lo this invention. may for instance or other of'ihe following formulicz R. co 8 cooin v if more than. two molecular pi'opoi'tions of thev carboxylic acid compound enter the anthmquinonc residue, analogous compounds are obtained.

'fhccondensation products possess generally the following propei ties. They consolutions in concentrated sulfuric acid.

The coloring matters which can be obtained froin those of the aforesaid condensation products which contain a carboxyl group in the ortho position to the sulfur atom, probably possess a constitution corresponding, for instance, to one or other of the following, or analogous, formulzc The condensation to form the coloring matter is preferably effected by means of an acid condensing agent, such for instance as sulfuric acid, ruining sulfuric acid, chlorosulfonic acid, phosphoric anhydrid, aluminium chlorid, and zinc chlorid, and the condensation can. be carried out either in the presence or. absence of a suitable diluting agent. When concentrated sulfuric acid, or ot-l'i'er agent which is capable of bring ing about sulfonation, is used for ei'tecting the condensation, unsul'fonated products are, as a rule, obtained "when only a moderate reaction takes place, while by more energetic reaction. sulfonatcd products result. The unsulfonated products can, if desired, be subsequently treated with sulfonating agents and be converted into their sulfonic acid derivatives.

"The unsul'jonated products are capable of use as Vat coloring matters and yield from red to yellow shades of excellent fastness, they are insoluble in Water and in dilute acids and alkalis, while they are soluble in concentrated sulfuric acid yielding red to yellow solutions. In. particular, the coloring matter obtainable from anthraquinone-1.5-bis-thiosalicylic acid is, in the dry state, a red powder which yields a red solution in concentrated sulfuric acid and dyes cotton from the vat red shades. Its sulfouls shades.

acid also dyes wool. brilliant red The following examples Will serve to illustrate further how my invention (air be carried into practical eii'cct, but lbis not confined to these examples. The parts are by weight. Q

Example 1: Mix together one hundred parts of l. 5dichlor-anthi".quinone, one hundred and twenty-five parts of thiosalicylic acid, one hundred parts of caustic potash, and two thousand parts oi absolute alcohol. Boil the mixture till no unchanged dichloranthraquinone is noticeable, allow the mass to cool, collect, by filtering, the potassium saltof the anthraquinone 1.5 bis thiosalicylic acid which is obtained, dissolve in Water, and precipitate the new condensation product in the form of the free acid by the addi-.

tion of hydrochloric acid. When dry, the

-said product is an orange-yellow powder,

ditlicultly soluble in Water, readily soluble in dilute caustic soda, giving an orangeyellow solution, and soluble cold sulfuric acid, giving a bottle green solution. The solution in sulfuric acid containing boric acid is orange-browns Example 2: introduce one part of anthraquinone-l.5-bisthiosallicylic acid {chtainable from 1.5-dichlor -anthraquinone and so dium thiosalicylate) into fiye parts of turn ing sulfuric acid, containing twent three per cent. free 86,, while avoiding, as far as possible, a rise in temperature. The solution, which is at first violet, gradually be comes brown and finally (after standing for u some time) red. Then pour the reaction liquid into water and filter oll. and wash the product'which separates out in red flakes. When dry, it is a red powder which yields a red solution in concentrated sulfuric acid.

' On treating the product of the foregoing 'Example 2 with a sulfonating agent, fOI'lIlstance with warm fuming sulfuric acid, a sulfonic acid can be obtained which dyes wool brilliant red shades of great fastness.

In a similar manner, other analogous compounds can be obtained from the other condensation products hereinhctore mentioned.

Now what I claim isz 1. In the production of autln'aquinone thio'xanthones the process which consists in producing compounds o't'the antliracer e se-' ries possessing a constitution, corresponding to the formula A( Sit-(300E), in which A represents an anthraquinone residue, R represents an aromatic residue, n represents a number, by causing an acid-substituted anthraquinonc derivative to react upon an ortho-thiophenol-carboxylic acid body.

2. In the production of. anthraquinonedithioxanthones the process which consists in producing condensatioii products of the anthraquinone series by causing halogenated anthraquinone to react uponthiophenolortho-carboxylic acid.

3. In .the production of anthraqiunonedithioxanthoue the process which consists in producing anthraquinone 1.5 bis thiosalicylic acid by acting upon 1.5dichlor-antln'a' quinone with thiosalicylic acid.

t The process of producing ant-hraqut none-tilioxanthones by causing an acid-substiiuteil fllll'lll'iltilllilOllO derivative to react upon an ortho-lliioplienol-carboxylic acid boil and then subjecting the product thus obiainetlto the action of a condensing agent.

The n-ocess of producing coloring nalters of the ai'ithracene series beingfinth'ieaquinone-thioxanthones by causinga halogenat etl anthraquinone to react upon thiophenol- OltllO-CfilbOKYllC acid and then subjecting the product thus obtained to the action of a condensing agent. i

(3. The process of producing coloring matter of the anthracene "series being anthl'aquinonc- (lithioxanthone by reacting upon 1.5- LllClllOl anthraqiilinone with thiophenolortho-carboxylic acid and then treating the antliraquinone-l.5-bistliiosalicylic acid so obtained with a condensing agent.

7. 'As new articles of manufacture the coloring matters Which are anthraquinonethioxanthones, which coloring matters are insoluble in Water and in dilute acids and alkalis, are soluble in concentrated sulfuric acicl yielding red to yellow solutions, and

dye cotton from the vat yellow to red shades oi excellent fastness.

8., As a new article of llldlllll fl(itlli0 2111- thraquinone clitliioxanthonc corresponding to the torniula' which in the unsulfonateil state is insoluble in Water, and in dilute acids and alkalis, un t consists, when dry, of a red bowler which yields a red solution in concentrated sulfuric acid andurlyes cotton from a rat red shades of excellent fastness, and which, in the unsulfonatecl form dyes WUOl red.

In testimony whereof I have hereunto set my hand in the presence of two subscribing Witnesses.

OSCAR BALLZY.

Witnesses:

ERNEST R EHRHARDT, A. O. TITTMANN. 

